Ltmc polymerization of unsaturated monomers

ABSTRACT

A process for polymerizing unsaturated monomers is disclosed. The process comprises polymerizing, in the presence of a late transition metal catalyst (LTMC), a variety of unsaturated monomers which are traditionally, some of which are exclusively, made by free radical polymerizations. The LTMC polymerization provides the polymer with improved properties such as no free radical residue and narrow molecular weight distribution.

FIELD OF THE INVENTION

The invention relates to polymerization of unsaturated monomers. Moreparticularly, the invention relates to polymerization of unsaturatedmonomers with late transition metal catalysts (LTMC).

BACKGROUND OF THE INVENTION

Chain polymerization of unsaturated monomers can be divided into freeradical, ionic, and coordination polymerizations. Ionic polymerizationincludes anionic and cationic polymerizations. Cationic polymerizationis usually initiated by the Lewis acids such as BF₃. Polyisobutylenerubber is the commercially important polymer made by the cationicpolymerization. Anionic polymerization is usually initiated byalkyllithiums such as n-BuLi. Many anionic polymerizations are devoid ofany termination reaction, and they are thus called “living”polymerization. Living anionic polymerization has led to the creation ofthermoplastic elastomers such as SBS (styrene-butanediene-styrene blockcopolymers).

Coordination polymerization includes the Ziegler-Natta polymerizationand the metallocene or single-site polymerization. The Ziegler-Nattapolymerization is performed with zirconium or titanium salts, such asTiCl₄, ZrCl₄, and VCl₄, as catalysts and alkyl aluminum compounds, suchas trimethyl aluminum, as cocatalysts. Metallocene catalyst wasdiscovered by Kaminsky in the early 1980's (see U.S. Pat. Nos. 4,404,344and 4,431,788). Metallocene catalyst comprises a transition metalcomplex that has one or more cyclopentadienyl (Cp) ligands. Unlike theZiegler-Natta catalysts which have multiple active sites ofpolymerization, metallocene catalysts have only “single” polymerizationsite, and therefore they are called “single-site” catalysts. Manynon-metallocene single-site catalysts have also been developed over thepast decade.

Among the chain polymerizations, free radical polymerization is the mostwidely used in the polymer industry. Commonly used free radicalinitiators include peroxides, azo compounds, and persulfates. Unlikeionic initiators or coordination catalysts which require restrictedconditions such as moisture and impurity free reaction systems, freeradical polymerization can readily tolerate moisture and impurities.More importantly, free radical polymerization can tolerate functionalmonomers such as hydroxyl, carboxyl, and amino monomers. Thus, freeradical polymerizations are exclusively used for making hydroxyl acrylicresins, polyacrylic acid, olefin-acrylic copolymers, and many otherfunctional polymers.

Since the late 1990s, olefin polymerization catalysts that incorporatelate transition metals (especially iron, nickel, or cobalt) and bulkyα-diimine ligands (or “bis(imines)”) have been investigated. These latetransition metal catalysts (LTMC) are of interest because, unlike theearly transition metal metallocenes or Ziegler catalysts, the LTMC canincorporate alkyl acrylate comonomers into polyolefins. See U.S. Pat.Nos. 5,866,663 and 5,955,555.

However, the LTMC is considered to be a coordination catalyst, and thusstudy on LTMC has been limited to olefin-related polymerizations. Noprior art discloses the use of LTMC for making hydroxyl acrylic resins,styrene-allyl alcohol copolymers, and many other important functionalpolymers. No prior act discloses the use of LTMC for the polymerizationof unsaturated monomers in the absence of olefins.

Compared to conventional free radical polymerization, the LTMC has greatpotential in tailoring of critical polymer properties: molecular weight,crystallinity or melting point, and polydispersity. Therefore, the LTMCmay provide better product quality and production consistency. Also, theLTMC does not require high temperature and high pressure polymerization.It avoids the use of explosive peroxides or azo compounds. Thus, theLTMC polymerization may provide a safer and more cost-effectivealternative to the existing free radical technology.

In summary, it is apparently important to explore the use of LTMC forthe polymerization of the unsaturated monomers which have beentraditionally, some of which have been exclusively, polymerized by freeradical polymerizations.

SUMMARY OF THE INVENTION

The process of the invention comprises polymerizing unsaturated monomersin the presence of a late transition metal catalyst (LTMC). The LTMCcomprises a Group 8-10 late transition metal complex and an activator.By “complex,” we mean the compounds which comprise a Group 8-10 metaland at least one polymerization-stable ligand which remains bound to themetal during the course of the polymerization process.

The process includes polymerizing one of the monomer groups (a) through(f): (a) a vinyl monomer selected from the group consisting of vinylaromatics, vinyl ethers, vinyl esters, and vinyl halides; (b) a vinylmonomer selected from the group consisting of vinyl ethers, vinylesters, and vinyl halides, and at least one olefin; (c) ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,and alkoxylated allylic alcohols, and at least one alkyl or arylacrylate or at least one alkyl or aryl methacrylate; (d) ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,and alkoxylated allylic alcohols, at least one alkyl or aryl acrylate orat least one alkyl or aryl methacrylate, and at least one olefin; (e) ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,and alkoxylated allylic alcohols, and at least one vinyl aromaticmonomer; or (f) a hydroxy-functional monomer selected from the groupconsisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates,allylic alcohols, and alkoxylated allylic alcohols, at least one vinylaromatic monomer, and at least one olefin.

DETAILED DESCRIPTION OF THE INVENTION

The process of the invention is polymerizing unsaturated monomers with alate transition metal catalyst (LTMC). The LTMC comprises a Group 8-10late transition metal complex and an activator. Suitable LTMC includethose known in the art.

Preferred late transition metal complexes have the general structure:LM(X)_(n)

The M is a Group 8-10 late transition metal. Preferably, the M isselected from the group consisting of Ni, Co, and Fe. More preferably,the M is Ni or Fe. Most preferably, the M is Fe.

The L is a polymerization-stable ligand. By “polymerization-stableligand,” we mean that the ligand remains bound to the metal during thecourse of the polymerization process. Preferably, the L is anisoindoline or bis(imine).

Suitable L ligands also include those taught by U.S. Pat. Nos. 5,714,556and 6,620,759, the teachings of which are herein incorporated byreference.

The X is a labile ligand. By “labile ligand,” we mean that the ligand iseasily displaceable during the polymerization. Preferably, L isindependently selected from the group consisting of hydrogen andhalides, and n, the number of the X ligands, is greater than or equal to1.

Suitable isoindoline ligands include those taught by co-pendingapplication Ser. No. 09/947,745, filed on Sep. 6, 2001, the teachings ofwhich are herein incorporated by reference. Preferably the isoindolineligands have the general structure:

When forming a late transition metal complex, the hydrogen of the N—Hgroup may be removed to form an ionic bonding between the nitrogen andthe late transition metal. Optionally, the aromatic ring hydrogen atomsof the above structure are independently substituted. Suitable ringsubstitute groups include alkyl, aryl, aralkyl, alkylaryl, silyl,halogen, alkoxy, aryloxy, siloxy, nitro, dialkyl amino, diaryl aminogroups, and the like.

A is an aryl or a heteroaryl group. When A is aryl, it preferably isphenyl- or alkyl-substituted, such as 4-methylphenyl or2,4,6-trimethylphenyl (2-mesityl). When A is heteroaryl, it ispreferably 2-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl,2-imidazolyl, 2-thiazolyl, or 2-oxazolyl. The aryl and heteroaryl groupscan be fused to other rings, as in a 2-naphthyl, 2-benzothiazolyl or2-benzimidazolyl group. A few exemplary isoindolines appear below:

Suitable bis(imine) ligands include those taught by U.S. Pat. No.5,866,663. Suitable bis(imine) ligands include those having the generalstructure:

wherein R¹ and R⁴ are each independently hydrocarbyl or substitutedhydrocarbyl. R² and R³ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R² and R³ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring.

Suitable bis(imine) ligands include those having the general structure:

R⁵ is hydrocarbyl or substituted hydrocarbyl, and R⁶ is hydrogen,hydrocarbyl or substituted hydrocarbyl, or R⁵ and R⁶ taken together forma ring. R⁹ is hydrocarbyl or substituted hydrocarbyl, and R⁸ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁹ and R⁸ takentogether form a ring. Each R⁷ is independently hydrogen, substitutedhydrocarbyl or hydrocarbyl, or two of R⁷ taken together form a ring; nis 2 or 3.

Suitable bis(imine) ligands include 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines), which are taught, e.g., byU.S. Pat. No. 5,955,555. The teachings of U.S. Pat. No. 5,955,555 areincorporated herein by reference.

Suitable bis(imine) ligands also include acenaphthenebis-N,N′-(2,6-diisopropylphenyl)imines, which are taught, e.g., by U.S.Pat. No. 6,127,497. The teachings of U.S. Pat. No. 6,127,497 areincorporated herein by reference.

Suitable activators include alumoxane and alkylaluminum compounds.Examples of suitable alumoxane compounds include methyl alumoxane (MAO),polymeric MAO (PMAO), ethyl alumoxane, diisobutyl alumoxane, and thelike. Examples of suitable alkylaluminum compounds includetriethylaluminum, diethyl aluminum chloride, trimethylaluminum,triisobutyl aluminum, and the like. Suitable alumoxane compounds alsoinclude those that are modified. Methods for the modification ofalumoxanes are known. For instance, U.S. Pat. No. 4,990,640 teaches themodification of alumoxanes with active hydrogen-containing compoundssuch as ethylene glycol. U.S. Pat. No. 6,340,771 teaches modifying MAOwith sugar to make “sweet” MAO. Also, U.S. Pat. No. 5,543,377 teachesmodifying alumoxanes with ketoalcohols and β-diketones. The teachings ofthese U.S. patents are incorporated herein by reference.

Suitable activators also include acid salts that containnon-nucleophilic anions. These compounds generally consist of bulkyligands attached to boron or aluminum. Examples include lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)aluminate, anilinium tetrakis(pentafluorophenyl)borate, and the like.

Suitable activators further include organoboranes, which are compoundsof boron and one or more alkyl, aryl, or aralkyl groups. Suitableorganoboranes include substituted and unsubstituted trialkyl andtriarylboranes such as tris(pentafluorophenyl)borane, triphenylborane,tri-n-octylborane, and the like. Suitable organoborane activators aredescribed in U.S. Pat. Nos. 5,153,157, 5,198,401, and 5,241,025. Theteachings of these U.S. patents are incorporated herein by reference.Suitable activators also include aluminoboronates, which are thereaction products of alkyl aluminum compounds and organoboronic acids.These activators are described in U.S. Pat. Nos. 5,414,180 and5,648,440, the teachings of which are incorporated herein by reference.

The late transition metal complex, the activator, or both are optionallysupported onto an inorganic solid or organic polymer support. Suitablesupports include silica, alumina, silica-aluminas, magnesia, titania,clays, zeolites, or the like. The support is preferably treatedthermally, chemically, or both prior to use to reduce the concentrationof surface hydroxyl groups. Thermal treatment consists of heating (or“calcining”) the support in a dry atmosphere at elevated temperature,preferably greater than about 100° C., and more preferably from about150° C. to about 600° C., prior to use. A variety of different chemicaltreatments can be used, including reaction with organo-aluminum,-magnesium, -silicon, or -boron compounds. See, for example, thetechniques described in U.S. Pat. No. 6,211,311.

The invention includes a process for polymerizing, in the presence ofthe LTMC, a vinyl monomer selected from the group consisting of vinylaromatics, vinyl ethers, vinyl esters, vinyl halides, the like, andmixtures thereof. Surprisingly, we found that these vinyl monomers,which are traditionally polymerized by free radical polymerization, canbe readily polymerized by the LTMC without the presence of any olefincomonomer.

Suitable vinyl aromatic monomers preferably have a —CR′═CH₂ groupconnected to an aromatic group. R′ is hydrogen or a C₁ to C₁₀ alkylgroup. Examples of suitable vinyl aromatic monomers are styrene,α-methylstyrene, p-methylstyrene, p-t-butylstyrene, chloromethylstyrene,trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene,methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene,chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene,pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene,fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene,4-fluoro-3-trifluoromethylstyrene, 9-vinylanthracene,2-vinylnaphthalene, the like, and mixtures thereof. Styrene isparticularly preferred.

Suitable vinyl ethers include vinyl alkyl ethers, vinyl aryl ethers, andmixtures thereof. Examples of suitable vinyl alkyl ethers are methylvinyl ether, ethyl vinyl ether, hexyl vinyl ether, octyl vinyl ether,decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,ethoxyethyl vinyl ether, chloroethyl vinyl ether,1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether,hydroxyethyl vinyl ether, dimethylaminoethyl vinyl ether,diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinylether, tetrahydrofurfuryl vinyl ether, and the like, and mixturesthereof. Examples of suitable vinyl aryl ethers are vinyl phenyl ether,vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenylether, vinyl naphthyl ether, vinyl anthranyl ether, the like, andmixtures thereof.

Suitable vinyl esters include vinyl acetate, vinyl butyrate, vinylisobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinylvalerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate,vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinylacetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinylchlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate, thelike, and mixtures thereof.

Suitable vinyl halides include by halogen substituted ethylenes.Examples are vinyl chloride, vinyl fluoride, vinylidene chloride,chlorotrifluoro ethylene, the like, and mixtures thereof.

The invention includes a process for polymerizing an olefin and a vinylmonomer selected from the group consisting of vinyl ethers, vinylesters, vinyl halides, the like, and mixtures thereof. Suitable vinylethers, vinyl esters and vinyl halides are discussed above. Suitableolefins include α-olefins, cyclic olefins, and mixtures thereof. C₂-C₁₀α-olefins are preferred. Ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-octene, and mixtures thereof are particularly preferred.Ethylene and propylene are most preferred.

The invention includes a process for polymerizing a hydroxy-functionalmonomer selected from the group consisting of hydroxyalkyl acrylates,hydroxyalkyl methacrylate, allylic alcohols, alkoxylated allylicalcohols, and mixtures thereof, and an alkyl or aryl acrylate or analkyl aryl methacrylate.

Suitable hydroxyalkyl acrylates and methacrylates include hydroxyethylacrylate and methacrylate, hydroxypropyl acrylate and methacrylate, andhydroxybutyl acrylate and methacrylate. Suitable allylic alcohols andalkoxylated allylic alcohols include allyl alcohol, methallyl alcohol,ethoxylated allyl alcohol, ethoxylated methallyl alcohol, propoxylatedallyl alcohol, and propoxylated methallyl alcohol. Suitable alkyl oraryl acrylates and methacrylates include C₁-C₂₀ alkyl acrylates andmethacrylates, C₆-C₂₀ aryl acrylates and methacrylates, the like, andmixtures thereof. Examples are n-butyl acrylate, n-butyl methacrylate,methyl methacrylate, t-butyl methacrylate, iso-butyl methacrylate,benzyl methacrylate, cyclohexyl methacrylate, the like, and mixturesthereof.

The invention includes a process for polymerizing a vinyl aromatic and ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,alkoxylated allylic alcohols, and mixtures thereof. Suitablehydroxyalkyl acrylates and methacrylates, allylic alcohols, alkoxylatedallylic alcohols, and vinyl aromatics are discussed above.

The invention also includes a process for polymerizing an olefin, avinyl aromatic, and a hydroxy-functional monomer selected from the groupconsisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates,allylic alcohols, alkoxylated allylic alcohols, and mixtures thereof.Suitable olefins, hydroxyalkyl acrylates and methacrylates, allylicalcohols, alkoxylated allylic alcohols, and vinyl aromatics arediscussed above.

The polymerization of the invention is preferably conducted at atemperature within the range of about 0° C. to about 200° C. Thepolymerization temperature varies depending on the polymers to be made.For example, making hydroxyl acrylic resins or styrene-allyl alcoholcopolymers requires a relatively high temperature (from about 80° C. toabout 150° C. is preferred). High polymerization temperatures lead tolow molecular weight resins which are suitable for high solids or lowVOC (volatile organic compound) coatings.

The polymerization can be performed in bulk, solution, slurry, or anyother suitable forms, depending on the polymers to be made. Forinstance, when a styrene-allyl alcohol copolymer is made, a bulkpolymerization is preferred because allyl alcohol polymerizes slowly andthe excess allyl alcohol functions as a solvent to control thepolymerization. When a hydroxyl acrylic resin is made from anhydroxyalkyl acrylate and alkyl acrylate, the polymerization ispreferably performed in solution wherein the solvent is used as a chaintransfer agent to lower the polymer molecular weight and to control thepolymerization rate.

The polymerization can be performed in a batch, semi-batch, orcontinuous process depending on the monomers used and the polymers made.For instance, a semi-batch process is preferred when a styrene-allylalcohol copolymer is made. In the semi-batch process, allyl alcohol isinitially charged into the reactor, and styrene is gradually fed intothe reactor during the polymerization. The gradual addition of styreneensures an even distribution of the OH function groups along the polymerchain.

The invention includes the polymers made by the process of theinvention. Particularly interesting polymers include hydroxyl acrylicresins (i.e., copolymers comprise hydroxyl-functional monomers, alkyl oraryl acrylates or alkyl or acryl methacrylates, and optionally vinylaromatics), olefin-acrylic copolymers, olefin-vinyl ester copolymers,and vinyl aromatic-allylic alcohol copolymers. The polymers made by theinvention differ from the polymers made by the free radicalpolymerization in that the polymers of the invention do not containresidual free radical initiators or fragments from the initiatordecomposition. Polymers made by free radical polymerization arethermally, chemically, or photo-chemically instable because of theresidual initiator or initiator fragments. Thus, the polymers of theinvention are expected to have improved thermal, chemical, andphoto-chemical resistance.

The invention also includes articles made from the polymers of theinvention. Examples of the useful articles which can be made from thepolymers of the invention include films, sheets, containers, pipes,fibers, coatings, adhesives, elastomers, sealants, and the likes. Oneadvantage of the invention is that the LTMC provide better tailoringthan the free radical polymerization in controlling the polymerproperties such as density, molecular weight, and molecular weightdistribution. For instance, the LTMC polymerization can provide hydroxylacrylic resins with narrow molecular weight distribution. The narrowmolecular weight distribution results in lower VOC or higher solidscoatings.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

EXAMPLE 1 Copolymerization of Ethylene, n-Butyl Acrylate, and AllylMonopropoxylate with Iron(II) 1,3-Bis(2-Mesitylimino)isoindoline Complexand Mao Activator

Catalyst Complex Preparation

A 100-mL round-bottom flask equipped with a nitrogen inlet and aninternal fritted-glass filter is charged with phthalimide (2.94 g, 20.0mmol) and ethyl acetate (60 mL). 2,4,6-Trimethylaniline (5.41 g, 40.0mmol, 2.0 eq.) and iron(II) chloride (2.54 g, 20.0 mmol) are added tothe flask, and the mixture is stirred under nitrogen at room temperaturefor 1 h. The yellow mixture is heated to reflux (77° C.) for 10 h, andis then stirred at room temperature for 32 h. A brown precipitate forms.The reaction mixture is concentrated by stripping out the ethyl acetateunder a stream of nitrogen. Cold diethyl ether (30 mL) is added to theresidue, and the mixture is stirred to wash the residue. The glassfilter is immersed in the liquid phase, which is then removed at reducedpressure through the internal filter. The solids are dried under vacuumfor 2 h to give a brown powder.

Polymerization

The polymerization is performed in an Endeavor (Advantage™ Series 3400Process Chemistry Workstation, made by Argonaut Technologies, Inc.). TheEndeavor contains eight pressure reactor tubes each with individualtemperature, pressure, stirring, and injection controls. The Endeavor isplaced in a glove box for manual manipulations and an inert atmosphereof nitrogen. A pre-programmed computer monitors and collects data onpressure, temperature, ethylene consumption in each reactor tube as afunction of the reaction time.

A reactor tube (10 mL) is charged with n-butyl acrylate (2 mL), allylmonopropoxylate (2 mL), tri-isobutyl aluminum (0.1 mL, 1.0 M hexanesolution), MAO (0.08 mL, 1.0 M toluene solution), and the catalystcomplex (0.2 mL, 1.0 mg/ml toluene solution). The reactor tube is thensealed. The reactor is pressured with ethylene to 400 psig and heated to100° C. The polymerization continues at these temperature and pressurereadings for about 1 h with continuous feeding of ethylene. The ethyleneconsumption is about 0.02 g. After polymerization, the unreactedmonomers are removed by vacuum, yielding 0.4 g of polymer. The polymerhas Mw: 5650; Mn: 3220; and Mw/Mn: 1.75.

EXAMPLE 2 Copolymerization of Ethylene, n-Butyl Acrylate, andHydroxyethyl Acrylate with Iron(II) 1,3-Bis(2-Mesitylimino)isoindolineComplex and Mao Activator

The general procedure of Example 1 is followed. A reactor tube (10 mL)is charged with n-butyl acrylate (2 mL), hydroxyethyl acrylate (2 mL),tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO (0.08 mL, 1.0M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg/ml toluenesolution). The reactor tube is then sealed. The reactor is pressuredwith ethylene to 400 psig and heated to 100° C. The polymerizationcontinues at these temperature and pressure readings for about 1 h withcontinuous feeding of ethylene. The ethylene consumption is about 0.2 g.After polymerization, unreacted monomers are removed by vacuum, yielding2.2 g of polymer.

EXAMPLE 3 Copolymerization of n-Butyl Acrylate and Allyl Monopropoxylatewith Iron(II) 1,3-Bis(2-Mesitylimino)isoindoline Complex and MaoActivator

The general procedure of Example 1 is followed. A reactor tube (10 mL)is charged with n-butyl acrylate (2 mL), allyl monopropoxylate (2 mL),tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO (0.08 mL, 1.0M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg/ml toluenesolution). The reactor tube is then sealed. The reactor contents areheated to 100° C. The polymerization continues at this temperaturereading for about 1 h. After polymerization, the unreacted monomers areremoved by vacuum, yielding 2.1 g of polymer.

EXAMPLE 4 Copolymerization of n-Butyl Acrylate and Hydroxyethyl acrylatewith Iron(II) 1,3-Bis(2-Mesitylimino)isoindoline Complex and MaoActivator

The general procedure of Example 1 is followed. A reactor tube (10 mL)is charged with n-butyl acrylate (2 mL), hydroxyethyl acrylate (2 mL),tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO (0.08 mL, 1.0M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg/ml toluenesolution). The reactor tube is then sealed. The reactor contents areheated to 100° C. The polymerization continues at this temperaturereading for about 1 h. After polymerization, the unreacted monomers areremoved by vacuum, yielding 3.4 g of polymer.

EXAMPLE 5 Copolymerization of Ethylene, Styrene, and AllylMonopropoxylate with Iron(II) 1,3-Bis(2-Mesitylimino)isoindoline Complexand Mao Activator

The general procedure of Example 1 is followed. A reactor tube (10 mL)is charged with styrene (2 mL), allyl monopropoxylate (2 mL),tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO (0.08 mL, 1.0M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg/ml toluenesolution). The reactor tube is then sealed. The reactor is pressuredwith ethylene to 400 psig and heated to 100° C. The polymerizationcontinues at these temperature and pressure readings for about 1 h withcontinuous feeding of ethylene. The ethylene consumption is about 0.01g. After polymerization, the unreacted monomers are removed by vacuum,yielding 0.23 g of polymer.

EXAMPLE 6 Copolymerization of Styrene and Allyl Monopropoxylate withIron(II) 1,3-Bis(2-Mesitylimino)isoindoline Complex and Mao Activator

The general procedure of Example 1 is followed. A reactor tube (10 mL)is charged with styrene (2 mL), allyl monopropoxylate (2 mL),tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO (0.08 mL, 1.0M toluene solution), and the catalyst (0.2 mL, 1.0 mg/ml toluenesolution). The reactor tube is then sealed. The reactor contents areheated to 100° C. The polymerization continues at this temperaturereading for about 1 h. After polymerization, the unreacted monomers areremoved by vacuum, yielding 0.1 g of polymer.

EXAMPLE 7 Copolymerization of Ethylene, n-Butyl Acrylate and AllylMonopropoxylate with Iron(II) 1,3-Bis(2-pyridylimino)isoindoline Complexand MAO Activator

Catalyst Preparation

A 100-mL round-bottom flask equipped with a nitrogen inlet and aninternal fritted-glass filter is charged with phthalimide (2.94 g, 20.0mmol) and ethyl acetate (50 mL). 2-Aminopyridine (3.77 g, 40.0 mmol, 2.1eq.) and iron(II) chloride (2.54 g, 20.0 mmol) are added to the flask,and the mixture is stirred under nitrogen at room temperature for 1 h.The mixture is stirred at room temperature for 120 h, yielding a whiteprecipitate. After washing with cold diethyl ether (3×20 mL), the whitesolids are dried under vacuum for 1 h.

Polymerization

The polymerization procedure of Example 1 is followed, but the aboveprepared catalyst complex is used. The ethylene consumption is 0.01 g,and 0.15 g of polymer is collected.

EXAMPLE 8 Copolymerization of Ethylene, n-Butyl Acrylate, and AllylMonopropoxylate with Iron(II) Bis(imine) Complex and MAO Activator

Catalyst Preparation

An iron(II) bis(imine) complex is prepared according Example 1 of U.S.Pat. No. 6,562,973. A 100-mL round-bottom flask equipped with a nitrogeninlet and an internal fritted-glass filter is charged with2,6-diacetylpyridine (2.00 g, 12.2 mmol) and ethyl acetate (50 mL).2,4,6-Trimethylaniline (3.52 g, 26.0 mmol, 2.13 eq.) is added to thestirred solution.

Iron(II) chloride (1.55 g, 12.2 mmol) is added to the flask, and themixture is stirred under nitrogen at room temperature for 42 h. Thereaction mixture is concentrated by stripping out solvents under reducedpressure. Cold diethyl ether (30 mL) is added to the residue, and themixture is stirred to wash the residue. The glass filter is immersed inthe liquid phase, which is then removed at reduced pressure through theinternal filter. The complex solids are dried under vacuum for 1 h.

Polymerization

The polymerization procedure of Example 1 is followed, but the aboveprepared catalyst complex is used. The ethylene consumption is 0.01 gand 0.17 g of polymer is collected. The polymer has Mw: 6000; and Mn:2170; and Mw/Mn: 2.76.

1. A process comprising polymerizing, in the presence of a Group 8-10metal complex and an activator, one of the monomer groups (a) through(f): (a) a vinyl monomer selected from the group consisting of vinylaromatics, vinyl ethers, vinyl esters, and vinyl halides thereof; (b) avinyl monomer selected from the group consisting of vinyl ethers, vinylesters, and vinyl halides, and at least one olefin; (c) ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,and alkoxylated allylic alcohols, and at least one alkyl or arylacrylate or at least one alkyl or aryl methacrylate; (d) ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,and alkoxylated allylic alcohols, at least one alkyl or aryl acrylate orat least one alkyl or aryl methacrylate, and at least one olefin; (e) ahydroxy-functional monomer selected from the group consisting ofhydroxyalkyl acrylates, hydroxyalkyl methacrylates, allylic alcohols,and alkoxylated allylic alcohols, and at least one vinyl aromaticmonomer; or (f) a hydroxy-functional monomer selected from the groupconsisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates,allylic alcohols, and alkoxylated allylic alcohols, at least one vinylaromatic monomer, and at least one olefin; wherein the complex has thegeneral structure:LM(X)_(n) wherein M is a Group 8-10 metal; L is a polymerization-stableligand selected from isoindolines or bis(imines); X is a labile ligand;and n is greater than or equal to 1; and wherein L is an isoindolineligand having the general structure:

wherein A and A′ are the same or different aryl or heteroaryl groups. 2.(canceled)
 3. (canceled)
 4. The process of claim 1 wherein A and A′ areidentical aryl groups.
 5. The process of claim 1 wherein A and A′ areidentical heteroaryl groups.
 6. The process of claim 1 wherein the M isFe and L is a 1,3-bis(2-mesitylimino)isoindoline or a1,3-bis(2-pyridylimino)isoindoline.
 7. The process of claim 1 whereinthe activator is selected from the group consisting of alkyl alumoxanes,alkylaluminum compounds, aluminoboronates, organoboranes, ionic borates,and ionic aluminates.
 8. (canceled)
 9. (canceled)
 10. A process whichcomprises polymerizing, in the presence of a Group 8-10 metal complexand an activator, a hydroxy-functional monomer selected from the groupconsisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates,allylic alcohols, and alkoxylated allylic alcohols, at least one alkylor aryl acrylate or at least one alkyl or aryl methacrylate, optionallya vinyl aromatic monomer, and optionally a C₂₋₁₀ α-olefin; wherein thelate transition metal complex comprises Fe and a1,3-bis(2-mesitylimino)isoindoline or a1,3-bis(2-pyridylimino)isoindoline ligand.
 11. The process of claim 10wherein the hydroxy-functional monomer is selected from the groupconsisting of hydroxyethyl acrylate, hydroxypropyl acrylate,hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutylacrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol,propoxylated allyl alcohol, and ethoxylated allyl alcohol.
 12. Theprocess of claim 10 wherein at least one of the alkyl or aryl acrylate,or the alkyl or aryl methacrylate, is selected from the group consistingof n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate,2-ethylhexyl methacrylate, methyl acrylate, methyl methacrylate, t-butylacrylate, t-butyl methacrylate, iso-butyl acrylate, iso-butylmethacrylate, iso-bornyl acrylate, and iso-bornyl methacrylate.
 13. Theprocess of claim 10 wherein the hydroxy-functional monomer is allylmonopropoxylate and the alkyl acrylate or methacrylate is n-butylacrylate or n-butyl methacrylate.
 14. The process of claim 10 whereinthe vinyl aromatic monomer is selected from the group consisting ofstyrene, □-methyl styrene, p-methyl styrene, and p-t-butyl styrene. 15.The process of claim 10 wherein the α-olefin is selected from the groupconsisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and1-octene.
 16. The process of claim 10 wherein the activator is an alkylalumoxane.
 17. (canceled)
 18. (canceled)
 19. A process which comprisespolymerizing, in the presence of a Group 8-10 metal complex and anactivator, at least one vinyl ester and at least one C₂₋₁₀ α-olefin. 20.The process of claim 19 wherein the vinyl ester is vinyl acetate and theα-olefin is ethylene.
 21. (canceled)
 22. (canceled)
 23. A process whichcomprises polymerizing, in the presence of a Group 8-10 metal complexand an activator, a hydroxy-functional monomer selected from the groupconsisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates,allylic alcohols, and alkoxylated allylic alcohols, at least one vinylaromatic monomer, and optionally at least one C₂₋₁₀ α-olefin.
 24. Theprocess of claim 23 wherein the vinyl aromatic monomer is styrene andthe hydroxy-functional monomer is selected from the group consisting ofallyl alcohol, methallyl alcohol, alkoxylated allyl alcohol, andalkoxylated methallyl alcohol.
 25. (canceled)
 26. (canceled)